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Register a new userExperimental determination of ferric iron partitioning between pyroxene and melt at 100KPa
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Pyroxene is the principal host of Fe$^{3+}$ in basalt source regions, hosting 79 and 81% of the Fe$^{3+}$ in spinel and garnet lherzolite, respectively, with opx and cpx hosting 48% and 31%, respectively, of the total Fe$^{3+}$ in spinel peridotite. To better understand partitioning of Fe$^{3+}$ between pyroxene and melt we conducted experiments at 100 KPa with f$_{O2}$ controlled by CO-CO$_2$ gas mixes between $Delta$QFM -1.19 to +2.06 in a system containing andesitic melt saturated with opx or cpx only. To produce large (100-150 $mu$m), homogeneous pyroxenes, we employed a dynamic cooling technique with a 5-10$deg$C/h cooling rate, and initial and final dwell temperatures 5-10$deg$C and 20-30$^circ$C super and sub-liquidus, respectively. Resulting pyroxene crystals have absolute variation in Al$_2$O$_3$ and TiO$_2$ <0.05 wt.% and <0.02 wt.%, respectively. Fe$^{3+}$/Fe$^T$ in pyroxenes and quenched glass were measured by XANES. We used a newly developed XANES calibration for cpx and opx by only selecting spectra with X-ray vibrating on the optic axial plane at $50 pm 5^circ$ to the crystallographic c axis. Values of DFe$^{3+}$ cpx/melt increase from 0.03 to 0.53 as fO2 increases from $Delta$QFM -0.44 to 2.06, while DFe$^{3+}$ opx/melt remains unchanged at 0.26 between $Delta$QFM -1.19 to +1.37. In comparison to natural peridotitic pyroxenes, Fe$^{3+}$/FeT in pyroxenes crystallized in this study are lower at similar f$_{O2}$, presumably owing to lower Al$^{3+}$ contents. This study shows that the existing thermodynamic models implemented in pMELTS and Perple_X over-predict the stability of Fe$^{3+}$ in pyroxenes, causing an anomalous reduced character to spinel peridotites at calculated conditions of MORB genesis.
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The crystal structure of iron in the Earths inner core remains debated. Most recent experiments suggest a hexagonal-close-packed (hcp) phase. In simulations, it has been generally agreed that the hcp-Fe is stable at inner core pressures and relatively low temperatures. At high temperatures, however, several studies suggest a body-centered-cubic (bcc) phase at the inner core condition. We have examined the crystal structure of iron at high pressures over 2 million atmospheres (>200GPa) and at high temperatures over 5000 kelvin in a laser-heated diamond cell using microstructure analysis combined with $textit{in-situ}$ x-ray diffraction. Experimental evidence shows a bcc-Fe appearing at core pressures and high temperatures, with an hcp-bcc transition line in pressure-temperature space from about 95$pm$2GPa and 2986$pm$79K to at least 222$pm$6GPa and 4192$pm$104K. The trend of the stability field implies a stable bcc-Fe at the Earths inner core condition, with implications including a strong candidate for explaining the seismic anisotropy of the Earths inner core.
We present new experimental data on major and trace element partition coefficients between alkali feldspar and trachytic melt. Experiments were conducted at 500 MPa, 870 890 {deg}C to investigate through short disequilibrium and long near equilibrium experiments the influence of diffusive re-equilibration on trace element partitioning during crystallization. Our data show that Ba and Sr behave compatibly, and their partition coefficients are influenced by re-equilibration time, orthoclase (Or) content, growth rate and cation order-disorder. High field strength elements (HFSE) and rare earth elements (except Eu) are strongly incompatible, but alkali feldspar efficiently fractionates light (LREE) from heavy rare earth elements (HREE). Our crystallization experiments reveal a strong influence of disequilibrium crystal growth on the partitioning of Ba and Sr. In particular, short-duration experiments show that rapid alkali feldspar crystal growth after nucleation, promotes disordered growth and less selectivity in the partitioning of compatible trace elements that easily enter the crystal lattice (e.g., Ba and Sr)....
The Earth acts as a gigantic heat engine driven by decay of radiogenic isotopes and slow cooling, which gives rise to plate tectonics, volcanoes, and mountain building. Another key product is the geomagnetic field, generated in the liquid iron core by a dynamo running on heat released by cooling and freezing to grow the solid inner core, and on chemical convection due to light elements expelled from the liquid on freezing. The power supplied to the geodynamo, measured by the heat-flux across the core-mantle boundary (CMB), places constraints on Earths evolution. Estimates of CMB heat-flux depend on properties of iron mixtures under the extreme pressure and temperature conditions in the core, most critically on the thermal and electrical conductivities. These quantities remain poorly known because of inherent difficulties in experimentation and theory. Here we use density functional theory to compute these conductivities in liquid iron mixtures at core conditions from first principles- the first directly computed values that do not rely on estimates based on extrapolations. The mixtures of Fe, O, S, and Si are taken from earlier work and fit the seismologically-determined core density and inner-core boundary density jump. We find both conductivities to be 2-3 times higher than estimates in current use. The changes are so large that core thermal histories and power requirements must be reassessed. New estimates of adiabatic heat-flux give 15-16 TW at the CMB, higher than present estimates of CMB heat-flux based on mantle convection; the top of the core must be thermally stratified and any convection in the upper core driven by chemical convection against the adverse thermal buoyancy or lateral variations in CMB heat flow. Power for the geodynamo is greatly restricted and future models of mantle evolution must incorporate a high CMB heat-flux and explain recent formation of the inner core.
During the last few years a number of works have proposed that planetary harmonics regulate solar oscillations and the Earth climate. Herein I address some critiques. Detailed analysis of the data do support the planetary theory of solar and climate variation. In particular, I show that: (1) high-resolution cosmogenic 10Be and 14C solar activity proxy records both during the Holocene and during the Marine Interglacial Stage 9.3 (MIS 9.3), 325-336 kyr ago, present four common spectral peaks at about 103, 115, 130 and 150 yrs (this is the frequency band that generates Maunder and Dalton like grand solar minima) that can be deduced from a simple solar model based on a generic non-linear coupling between planetary and solar harmonics; (2) time-frequency analysis and advanced minimum variance distortion-less response (MVDR) magnitude squared coherence analysis confirm the existence of persistent astronomical harmonics in the climate records at the decadal and multidecadal scales when used with an appropriate window length (110 years) to guarantee a sufficient spectral resolution. However, the best coherence test can be currently made only by comparing directly the temperature and astronomical spectra as done in Scafetta (J. Atmos. Sol. Terr. Phys. 72(13), 951-970, 2010). The spectral coherence between planetary, solar and climatic oscillations is confirmed at the following periods: 5.2 yr, 5.93 yr, 6.62 yr, 7.42 yr, 9.1 yr (main lunar tidal cycle), 10.4 yr (related to the 9.93-10.87-11.86 yr solar cycle harmonics), 13.8-15.0 yr, 20 yr, 30 yr and 61 yr, 103 yr, 115 yr, 130 yr, 150 yr and about 1000 year. This work responds to the critiques of Cauquoin et al. (Astron. Astrophys. 561, A132, 2014) who ignored alternative planetary theories of solar variations, and of Holm (J. Atmos. Sol. Terr. Phys. 110-111, 23-27, 2014) who used inadequate physical and time frequency analysis of the data.
Experimental studies of mantle petrology find that small concentrations of water and carbon dioxide have a large effect on the solidus temperature and distribution of melting in the upper mantle. However, it has remained unclear what effect small fractions of deep, volatile-rich melts have on melt transport and reactive melting in the shallow asthenosphere. Here we present theory and computations indicating that low-degree, reactive, volatile-rich melts cause channelisation of magmatic flow at depths approximately corresponding to the anhydrous solidus temperature. These results are obtained with a novel method to simulate the thermochemical evolution of the upper mantle in the presence of volatiles. The method uses a thermodynamically consistent framework for reactive, disequilibrium, multi-component melting. It is coupled with a system of equations representing conservation of mass, momentum, and energy for a partially molten grain aggregate. Application of this method in two-phase, three-component upwelling-column models demonstrates that it reproduces leading-order features of hydrated and carbonated peridotite melting; in particular, it captures the production of low-degree, volatile-rich melt at depths far below the volatile-free solidus. The models predict that segregation of volatile-rich, deep melts promotes a reactive channeling instability that creates fast and chemically isolated pathways of melt extraction. Reactive channeling occurs where volatile-rich melts flux the base of the silicate melting region, enhancing dissolution of fusible components from the ambient mantle. We find this effect to be similarly expressed for models of both hydrated and carbonated mantle melting. These findings indicate that despite their small concentrations, water and carbon dioxide have an important control on the extent and style of magma genesis, as well as on the dynamics of melt transport.
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